Process of inhibiting scale formation in aqueous systems using α-1,4-thiazine alkanephosphonic acids

ABSTRACT

This invention relates to α-1,4-thiazine alkanephosphonic acids; and to the preparation and uses thereof in inhibiting scale formation in aqueous systems.

This is a division, of application Ser. No. 932,257, filed Aug. 9, 1978,now U.S. Pat. No. 4,264,767.

This invention relates to novel α-1,4-thiazine alkanephosphonic acids ofthe formula: ##STR1## where R is a substituted group, for example, ahydrocarbon or a substituted hydrocarbon group such as alkyl,cycloalkyl, alkenyl, aryl, aralkyl, substituted aryl, etc.; R' ishydrogen or a substituted group, such as a hydrocarbon group, such asalkyl, etc.; Z is S, ##STR2## and M is hydrogen or a salt moiety forexample an alkali metal, alkaline earth metal, alkyl ammonium, ammonium,etc.; and to uses thereof.

It has been shown by A. Ford--Moore, J. Chem. Soc. 1949, p. 2433, whendivinyl sulfone is treated with primary amines, derivatives of1,4-thiazine-1,1-dioxide result. In the present invention I have reactedan α-aminoalkanephosphonic acid with an equal molar amount of a divinylsulfur compound to produce the novel α-1,4-thiazine alkanephosphonicacids. The reaction may be summarized by the following equation:##STR3##

Examples of the divinyl sulfur compounds are: ##STR4##

The α-aminoalkanephosphonic acids were synthesized by several methodsthat have been described by R. Tyka, Tetrahedron Lett. 1970, p. 677., J.Lukszo, R. Tyka, Synthesis 1977, p. 239, and R. Gancarz, Synthesis 1977,p. 635.

In carrying out the reaction it is preferred to carry out the reactionin a solvent or a mixture of solvents in which the α-amino phosphonicacid is soluble. To the solution of the α-amino phosphonic acid in asuitable solvent or mixture of solvents is slowly added the divinylsulfone. The preferred temperature is about 20° to 50° C. though higheror lower temperatures may be employed. A catalyst such as triethylaminemay be used. In most instances, upon cooling, the α-1,4-thiazinealkanephosphonic acid precipitates and is purified by recrystallization.In some cases it is necessary to reduce the final volume in order toisolate the desired product.

A particular object of the present invention is the use of theseproducts to inhibit scale formation in aqueous systems.

These products have a wide variety of uses such as in acid corrosioninhibitors, scale inhibitors, chelating agents, microbiocides, etc.

The invention may be illustrated by the following examples.

EXAMPLE 1

To a solution of α-aminoethylphosphonic acid 12.6 g. (0.1 mol) in 50 ml.of a 50:50 (by volume) mixture of ethanol and water was slowly added,with stirring, divinyl sulfone 11.8 g. (0.1 mol). The reaction mixturebecame warm and upon cooling deposited crystals. After cooling in an icebath, the crystalline product was filtered and washed with cold ethanol.The product was recrystallized from aqueous ethanol. The product had thefollowing structure which was characterized by H' and P⁻ NMR spectrum.##STR5##

Anal. Calcd. for C₆ H₁₄ O₅ NPS: P, 12.70; N, 5.74; S, 13.11.

Found: P, 12.59; N, 5.68; S, 13.21.

EXAMPLE 2

To a solution of α-aminopropylphosphonic acid 13.9 g. (0.1 mol) in 50ml. of aqueous ethanol was slowly added, with stirring, divinyl sulfone11.8 g. (0.1 mol). The reaction mixture became warm and depositedcrystals upon cooling. The product was filtered and washed with coldethanol. It was recrystalized from aqueous ethanol. It had the followingstructure. ##STR6##

Anal. Calcd. for C₇ H₁₆ O₅ NPS: P, 12.06; N, 5.45; S, 12.45. Found: P,12.00; N, 5.38; S, 12.33.

EXAMPLE 3

In a similar manner α-aminobenzylphosphonic acid 18.7 g. (0.1 mol) wasreacted with divinyl sulfone 11.8 g. (0.1 mol). The product was found tohave the following structure: ##STR7##

Anal. Calcd. for C₁₁ H₁₆ O₅ NPS: P, 10.16; N, 4.59; S, 10.49. Found: P,10.24; N, 4.61; S, 10.65.

To avoid repetitive detail, the following table was constructed tofurther illustrate examples of this invention that were prepared in asimilar manner.

    ______________________________________                                         ##STR8##                                                                     ______________________________________                                        Ex. 4   C.sub.3 H.sub.7 Ex. 8      C.sub.6 H.sub.13                           Ex. 5   C.sub.6 H.sub.5 CH.sub.2                                                                      Ex. 9      C.sub.11 H.sub.23                          Ex. 6                                                                                  ##STR9##       Ex. 10     C.sub.17 H.sub.33                          Ex. 7                                                                                  ##STR10##      Ex. 11     C.sub.17 H.sub.35                          ______________________________________                                    

USE AS A SCALE INHIBITOR

Scale formation from aqueous solutions containing an oxide variety ofscale forming compounds, such as calcium, barium and magnesiumcarbonate, sulfate, silicate, oxalates, phosphates, hydroxides,fluorides and the like are inhibited by the use of threshold amounts ofthe compositions of this invention which are effective in small amounts,such as less than 2.5 p.p.m.

The compounds of the present invention (i.e., the acid form of thecompounds) may be readily converted into the corresponding alkali metal,ammonium or alkaline earth metal salts by replacing at least half of thehydrogen ions in the phosphonic acid group with the appropriate ions,such as the potassium ion or ammonium or with alkaline earth metal ionswhich may be converted into the corresponding sodium salt by theaddition of sodium hydroxide. If the pH of the amine compound isadjusted to 7.0 by the addition of caustic soda, about one half of the--OH radicals on the phosphorus atoms will be converted into the sodiumsalt form.

The scale inhibitors of the present invention illustrate improvedinhibiting effect at high temperatures when compared to prior artcompounds. The compounds of the present invention will inhibit thedeposition of scale-forming alkaline earth metal compounds on a surfacein contact with aqueous solution of the alkaline earth metal compoundsover a wide temperature range. Generally, the temperatures of theaqueous solution will be at least 40° F., although significantly lowertemperatures will often be encountered. The preferred temperature rangefor inhibition of scale deposition is from about 130° to 350° F. Theaqueous solutions or brines requiring treatment generally contain about50 p.p.m. to about 50,000 p.p.m. of scale-forming salts. The compoundsof the present invention effectively inhibit scale formation whenpresent in an amount of from 0.1 to about 100 p.p.m., and preferably 0.2to 50 p.p.m. wherein the amounts of the inhibitor are based upon thetotal aqueous system. There does not appear to be a concentration belowwhich the compounds of the present invention are totally ineffective. Avery small amount of the scale inhibitor is effective to acorrespondingly limited degree, and the threshold effect is obtainedwith less than 0.1 p.p.m. There is no reason to believe that this is theminimum effective concentration. The scale inhibitors of the presentinvention are effective in both brine, such as sea water, and acidsolutions.

The following examples are presented to illustrate the use of thephosphonates prescribed herein and are presented for purposes ofillustration and not of limitation.

The following test was used to evaluate these compositions as scaleinhibitors.

Procedure:

1. Make up stock CaCl₂.2H₂ O,2.94 g/L or 56 g/5 gallons (18.9 liters)

2. Stock NaHCO₃ should be 3.35 g/L or 64 g/5 gallons.

3. Inhibitors--Make 0.1 percent solutions in deionized water. 1 ml in100 sample=10 p.p.m. (Test at 5, 20, and 50 p.p.m.).

Put 50 ml bicarbonate solution into 100 ml milk dilution bottle. Addinhibitor (for 100 ml final volume). Then add 50 ml CaCl₂ solution andset in bath at 180° F. Do not cap. Always prepare a blank. Run ahardness determination on a 50-50 mixture before heating.

Heat at 180° F. Take 10 ml samples from bottles after 2 hours and 4hours.

Filter through millipore filter.

Run total hardness on filtrate.

Calculate as % Ca still in solution, i.e., ##EQU1##

The compounds were tested at 180° F. at the concentration shown.Readings were taken after 2 and 4 hours.

                  TABLE A                                                         ______________________________________                                        Scale Inhibitor Tests                                                                           Concen-    % Protec-                                        Compound          tration    tion                                             ______________________________________                                        Example 1         5 p.p.m.   25                                                                 50 p.p.m.  45                                               Example 1 (sodium salt)                                                                         50 p.p.m.  44                                               Example 2         5 p.p.m.   30                                               Example 2 (sodium salt)                                                                         5 p.p.m.   31                                               Example 3 (sodium salt)                                                                         5 p.p.m.   25                                                                 50 p.p.m.  42                                               Example 4 (sodium salt)                                                                         5 p.p.m.   24                                                                 50 p.p.m.  43                                               Typical Commercial                                                                              5 p.p.m.   24%                                              Inhibitor         50 p.p.m.  30%                                              ______________________________________                                    

USE IN ACID SYSTEMS

The compounds of this invention can also be employed as corrosioninhibitors for acid systems, for example as illustrated by the picklingof ferrous metals, the treatment of calcareous earth formations, etc.,as described in the following sections.

USES

This invention also relates to the inhibition of corrosion, particularlythe corrosion of metals in contact with the acid solutions.

The present invention is especially useful in the acidizing or treatingof earth formations and wells traversed by a bore hole. It may also beused in metal cleaning and pickling baths which generally compriseaqueous solutions of inorganic acids such as sulfuric acid, hydrochloricacid, phosphoric acid and are useful in the cleaning and treatment ofiron, zinc, ferrous alloys, and the like.

If no corrosion inhibitor is present when the aqueous acidic solutioncomes in contact with the metal, excessive metal loss and consumption orloss of acid, and other adverse results will be experienced. There hasbeen a continuing search for corrosion inhibitors which can be usedeffectively in small concentrations, and which are economical toproduce. The need is also for corrosion inhibitors which are effectiveat high temperatures, e.g., 200° F. and above, such as are found inoperations involving acidic solutions, particularly oil-well acidizingwhere higher and higher temperatures are found as the well extendsfurther into the earth.

While the compounds of this invention are of themselves particularlygood acid corrosion inhibitors, optionally they may be blended withacetylenic alcohols, dispersing and solubilizing agents such asethoxylated phenols, alcohols, and fatty acids. They may also be blendedwith such known acid inhibitors as the quinoline or alkyl pyridinequaternary compounds or synergists such as terpene alcohols, formamide,formic acid, alkyl amine, alkylene polyamines, heterocyclic amines, andthe like.

Quaternary ammonium compounds may be illustrated by C-alkylpyridine-N-methyl chloride quaternary, C-alkyl pyridine-N-benzylchloride quaternary, quinoline-N-benzyl chloride quaternary,isoquinoline-N-benzyl chloride quaternary, thioalkyl pyridinequaternaries, thioquinoline quaternaries, benzoquinoline quaternaries,thiobenzoquinoline quaternaries, imidasole quaternaries, pyrimidinequaternaries, carbazole quaternaries, the corresponding ammoniumcompounds, pyridines and quinolines may also be used alone or incombination with the quaternary compounds. Thus a pyridine plusquinoline quaternary, a quinoline plus quinoline quaternary, orquinoline or amine alone or in combination may be used.

The formic acid compound may be selected from the esters and amides offormic acid. The formic acid compound may be from the group consistingof formate esters of the structure:

    HCOOR

where R is a monoaryl group, an alkyl group having 1 to 6 carbon atoms,cyclo-alkyl residues having 5 to 6 carbon atoms, alkenyl and alkynlgroups having 2 to 6 carbon atoms which may contain functional groupingsselected from --C--OH, --OH, ═C═O, --COOH, --SH, and NH₂. Examples ofthe formic acid compound are: methyl formate, ethylformate, benzylformate, other alkyl and aryl formates, and the like. Other examplesinclude formamide, dimethyl formamide, formanilide, and the like.Mixtures of the esters and mixtures of the amides may be used.

USE IN ACIDIZING EARTH FORMATIONS

The compositions of this invention can also be used as corrosioninhibitors in acidizing media employed in the treatment of deep wells toreverse the production of petroleum or gas therefrom and moreparticularly to an improved method of acidizing a calcareous ormagnesium oil-bearing formation.

It is well known that production of petroleum or gas from a limestone,dolomite, or other calcareous-magnesian formation can be stimulated byintroducing an acid into the producing well and forcing it into the oilor gas bearing formation. The treating acid, commonly a mineral acidsuch as HCl, is capable of forming water soluble salts upon contact withthe formation and is effective to increase the permeability thereof andaugment the flow of petroleum to the producing well.

Corrosion Test Procedure

In these tests the acid solutions were mixed by diluting concentratedhydrochloric acid with water to the desired concentrations.

Corrosion coupons of 1020 steel (AISI) were pickled in an uninhibited10% HCl solution for 10 minutes, neutralized in a 10% solution ofNaHCO₃, dipped in acetone to remove water and allowed to dry. They werethen weighed to the nearest milligram and stored in a desicator.

In most of the tests, a 25 cc/in² acid volume to coupon surface arearatio was used. After the desired amount of acid was poured into glassbottles, the inhibitor was added. The inhibited acid solution was thenplaced in a water bath which had been set at a predetermined temperatureand allowed to preheat for 20 minutes. After which time, the couponswere placed in the preheated inhibited acid solutions. The coupons wereleft in the acid solutions for the specified test time, the removed,neutralized, recleaned, rinsed, dipped in acetone, allowed to dry, thenreweighed.

The loss in weight in grams was multiplied times a calculated factor toconvert the loss in weight to lbs./ft² /24 hrs. The factor wascalculated as follows: ##EQU2##

    ______________________________________                                        CORROSION INHIBITION IN 15% HCl                                               Inhi-             Test     Test   Corrosion Rate                              bitor    p.p.m.   Temp.    Time   (lbs/ft.sup.2 /day)                         ______________________________________                                        Ex. 3    2000     150° F.                                                                         4 hrs. 0.075                                       Ex. 5    2000     150° F.                                                                         4 hrs. 0.065                                       Ex. 8    2000     150° F.                                                                         4 hrs. 0.062                                       Ex. 9    2000     150° F.                                                                         4 hrs. 0.042                                       Ex. 10   2000     150° F.                                                                         4 hrs. 0.035                                       Blank    2000     150° F.                                                                         4 hrs. 0.290                                       ______________________________________                                    

USE AS A MICROBIOCIDE (I) In water treatment

This phase of the present invention relates to the treatment of water.More particularly, it is directed to providing improved means forcontrolling microbiological organisms including bacteria, fungi, algae,protozoa, and the like, present in water.

It is well known that ordinary water contains various bacteria, fungi,algae, protozoa and other microbiological organisms which, ifuncontrolled, multiply under certain conditions so as to present manyserious problems. For example, in swimming pools the growth of thesemicrobiological organisms is very undesirable from a sanitary standpointas well as for general appearances and maintenance. In industrial watersystems such as cooling towers, condenser boxes, spray condensers, watertanks, basins, gravel water filters, and the like, microbiologicalorganisms may interfere greatly with proper functioning of equipment andresult in poor heat transfer, clogging of systems and rotting of woodenequipment, as well as many other costly and deleterious effects.

In other industrial applications where water is used in processes, asfor example, as a carrying medium, etc., microbiological organisms mayalso constitute a problem in maintenance and operation. Illustrative ofsuch industrial applications are the pulp and paper manufacturingprocesses, oil well flooding operations and the like.

The products of this invention are suitable as biocides for industrial,agricultural and horticultural, military, hygienic and recreationalwater supplies. They provide an inexpensive, easily prepared group ofproducts which can be used, in minimal amounts, in water supplies, incooling towers, air-conditioning systems, on the farm and ranch, in thefactory, in civilian and military hospitals and dispensaries, in camps,for swimming pools, baths and aquaria, waterworks, wells, reservoirs, byfire-fighting agencies, on maritime and naval vessels, in boilers,steam-generators and locomotives, in pulp and paper mills, forirrigation and drainage, for sewage and waste disposal, in the textileindustry, in the chemical industries, in the tanning industry, etcetera, and which will render said water supplies bactericidal,fungicidal and algicidal. They further provide a simple process wherebywater supplies, for whatever purposes intended, are renderedbacteriostatic, fungistatic and algistatic, i.e., said water suppliestreated by the process of this invention will resist and inhibit thefurther growth or proliferation of bacteria, fungi, algae and all formsof microbial life therein.

(II) Water flooding in secondary recovery of oil

This phase of the present invention relates to secondary recovery of oilby water flooding operations and is more particularly concerned with animproved process for treating flood water and oil recovery therewith.More particularly this invention relates to a process of inhibitingbacterial growth in the recovery of oil from oil-bearing strata by meansof water flooding taking place in the presence of sulfate-reducingbacteria.

Water flooding is widely used in the petroleum industry to effectsecondary recovery of oil. By employing this process the yield of oilfrom a given field may be increased beyond the 20-30 percent of the oilin a producing formation that is usually recovered in the primaryprocess. In flooding operation, water is forced under pressure throughinjection wells into or under oil-bearing formations to displace the oiltherefrom to adjacent producing wells. The oil-water mixture is usuallypumped from the producing wells into a receiving tank where the water,separated from the oil, is siphoned off, and the oil then transferred tostorage tanks. It is desirable in carrying out this process to maintaina high rate of water injection with a minimum expenditure of energy. Anyimpediment to the free entry of water into oil bearing formationsseriously reduces the efficiency of the recovery operation.

The term "flood water" as herein employed is any water injected into oilbearing formations for the secondary recovery of oil. In conventionaloperations, the water employed varies from relatively pure spring waterto brine and is inclusive of water reclaimed from secondary recoveryoperations and processed for recycling. The problems arising from thewater employed depend in part on the water used. However, particularlytroublesome and common to all types of water are problems directly orindirectly concerned with the presence of microorganisms, such asbacteria, fungi and algae. Microorganisms may impede the free entry ofwater into oil-bearing formations by producing ions susceptible offorming precipitates, forming slime and/or existing in sufficiently highnumbers to constitute an appreciable mass, thereby plugging the pores ofthe oil-bearing formation. Free plugging increases the pressurenecessary to drive a given volume of water into an oil-bearing formationand oftentimes causes the flooding water to by-pass the formation to beflooded. In addition, microorganisms may bring about corrosion by actingon the metal structures of the wells involved, producing corrosivesubstances such as hydrogen sulfide, or producing conditions favorableto destructive corrosion such as decreasing the pH or producing oxygen.The products formed as the result of corrosive action may also bepore-plugging precipitates. Usually, the difficulties encountered are acombination of effects resulting from the activity of differentmicroorganisms.

(III) Hydrocarbon treatment

This phase of the present invention relates to the use of thesecompounds as biocides in hydrocarbon systems.

In addition to being used as biocides in aqueous systems, the compoundsof this invention can also be employed as biocides in hydrocarbonsystems, particularly when petroleum products are stored. It is believedthat bacteria and other organisms, which are introduced into hydrocarbonsystems by water, feed readily on hydrocarbons resulting in a loss inproduct; that microorganisms cause the formation of gums, H₂ S,peroxides, acids and slimes at the interface between water and oil; thatbacterial action is often more pronounced with rolling motion than understatic conditions, etc. Loss of product, corrosion of the storage tank,clogging of filters and metering instruments, and fuel deterioration areamong the harmful effects of bacteria growth in fuels. The activity ofmicroorganism growth is often increased by the presence of rust. Notonly do these microorganisms often encourage rust but rust encouragesmicroorganism growth. Since microorganism growth appears to beconsiderably higher with kerosene than with gasoline, plugged filtersexperienced with jet fuels which contain large amounts of kerosene is aserious problem.

The compositions of this invention can be employed in hydrocarbonsystems.

MICROBIOCIDAL TESTING

The screening procedure was as follows: a one percent by weight solutionof the test compound in water was prepared. The solution was asepticallyadded to a sterile broth that would support the growth of the testorganism, Desulfovibro desulfuricans, to provide the specifiedconcentration given by weight of test compound per million parts byweight of broth. A general growth medium, such as prescribed by theAmerican Petroleum Institute was used. The broth containing the testcompound then was dispersed in 5 cc. amounts into sterile disposabletubes and the tubes were inoculated with the growing test organism andincubated at 35° C. for 24 hours. The absence or presence of growth ofthe microorganisms was determined by visual inspection by an experiencedobserver.

Following is a summary of the results of the testing of examples of thisinvention.

    ______________________________________                                        Compound      Concen-                                                         Example       tration                                                         Number        in p.p.m.   Results                                             ______________________________________                                        3 (Sodium salt)                                                                             75          gave control                                        9 (sodium salt)                                                                             25          gave control                                        10 (sodium salt)                                                                            50          gave control                                        ______________________________________                                         *By control is meant that the test compound was biostatic or biocidal         i.e., no growth of the test organism occured under the test conditions.  

I claim:
 1. A process of inhibiting scale formation in an aqueoussolution which comprises treating said aqueous solution with aneffective amount of a compound of the formula ##STR11## where R is amember selected from the group consisting of alkyl, alkenyl, cycloalkyl,aryl, alkaryl, aralkyl and hydroxyphenyl, and R' is hydrogen or alkyl, Zis S, SO or SO₂, and M is a hydrogen or a salt moiety.
 2. The process ofclaim 1 wherein R' is a hydrogen and Z is SO₂.
 3. The process of claim 1where R is methyl, ethyl, propyl, hexyl, undecyl, heptadecenyl,heptadecyl, phenyl, hydroxyphenyl, tolyl, benzyl or cyclohexyl.
 4. Theprocess of claim 1 where R is --CH₃, Z is SO₂ and M is H.
 5. The processof claim 1 where R is ##STR12## Z is SO₂ and M is H.
 6. The process ofclaim 1 where R is ##STR13## Z is SO₂ and M is H.
 7. The process ofclaim 1 where R is ##STR14## Z is SO₂ and M is H.
 8. The process ofclaim 1 where R is C₁₇ H₃₃ -, Z is SO₂ and M is H.